Straight-oil finishing composition and fiber yarn treated therewith

ABSTRACT

The invention relates to a straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiloxane oil or liquid paraffin having a viscosity of 3 to 70 mm 2 /s at 25 centigrade temperature; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups and wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C 3 H 7 SiO 3/2 . This composition is useful for treating fiber yarn.

The invention relates to a straight-oil finishing composition useful for treating fiber yarn which has improved storage stability and antistatic properties, and a fiber yarn treated with the straight-oil finishing composition.

Various silicones find wide application in compositions of straight-oil type treatment agents which receive their name because they are free of any water or solvents. For example, it was proposed to use a mixture of polyamylsiloxane and polydimethylsiloxane as a lubricity-improving agent for Spandex or similar elastic filaments (see Japanese Patent Publication (hereinafter referred to as Kokoku) No. Sho 42-8438). However, this oil-type treatment agent utilizes expensive polyamylsiloxane. Furthermore, production of polyamylsiloxane may be accompanied by variations in the amount of silanol groups contained in this composition, as well as by variations in antistatic properties. A yarn-treating composition obtained by combining a dimethylsiloxane oil with the product of copolymerization of an MQ-type silicone resin and a DT-type silicone resin (see Kokoku No. Sho 63-12197) is also known. A drawback of the aforementioned product of copolymerization of the silicone resins is that copolymerization of the silicone resin is difficult to control and that viscosity and antistatic properties of the obtained oil-type treatment agent are subject to variations.

One object of the invention to provide a straight-oil finishing composition, which has excellent storage stability and antistatic properties.

The present invention relates to a straight-oil finishing composition comprising

-   (A) 100 parts by weight of a polydimethylsiloxane oil or liquid     paraffin having a viscosity of 3 to 70 mm²/s at 25° C.; and -   (B) 0.5 to 100 parts by weight of an organopolysiloxane resin which     contains silanol groups and silicon-bonded alkoxy groups and 20 mole     % or more of all siloxane units are represented by the formula     C₃H₇SiO_(3/2).

Among other things, this straight-oil finishing composition is useful for treating fiber yarn.

Component (A) is a main component of the composition of the invention. Its function is to impart smoothness to the fiber yarn. It is recommended that the viscosity at 25° C. of the polydimethylsiloxane oil or liquid paraffin used in this component be within the range of 3 to 70 mm²/s, preferably 3 to 50 mm²/s, and even more preferably, 3 to 30 mm²/s. This is because, if the viscosity is below 3 mm²/s, the treated filament will have insufficient smoothness and if the viscosity exceeds 70 mm²/s, too much of the treatment agent will adhere to the fiber filament. The molecular structure of the polydimethylsiloxane oil of component (A) may be linear, cyclic, or partially branched. In the case of a linear or partially branched molecular structure, it is recommended to cap the molecular terminals with groups such as trialkylsiloxy or hydroxyl groups. The liquid paraffin useful in component (A) should have a high degree of purity, be colorless, and free of taste and odor.

Component (B) is a distinguishing component of the composition of the invention and comprises an organopolysiloxane resin which is compatible with component (A). It is required that 20 mole % or more of all siloxane units of this organopolysiloxane resin are represented by the formula C₃H₇SiO_(3/2) and that each molecule of the aforementioned resin contain one or more silanol groups and one or more silicon-bonded alkoxy groups. It is recommended that, in addition to the aforementioned siloxane units, this component contain siloxane units of formula C₃H₇ (HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), where each R′ is an independently selected from alkyl group having 1 to 8 carbon atoms and alkyloxyalkylene group having 1 to 8 carbon atoms. Examples of alkyl groups useful as R′ include methyl, ethyl, propyl, butyl, hexyl, and octyl. Examples of alkyloxyalkylene groups useful as R′ include methoxyethylene, and ethoxyethylene. Most preferably from the point of view of better compatibility with component (A), the R′ groups are independently selected from all groups having 3 to 8 carbon atoms and alkyloxyalkylene groups having 3 to 8 carbon atoms, with alkyl groups having 3 to 8 carbon atoms being even more preferable. In the above formula, 0<a≦2; 0<b≦2 and 0<(a+b)≦2. It is recommended that the amount of silanol groups contained in component (B) be greater than the amount of alkoxy groups so a>b. Siloxane units of formula C₃H₇SiO_(3/2) preferably comprise 20 to 95 mole % of all siloxane units, while siloxane units of formula C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2) preferably comprise 5 to 80 mole % of all siloxane units. The sum of both siloxane units should be 40 mole % or more of all siloxane units and preferably should occupy 60 to 100 mole %.

The organopolysiloxane resin can be represented by the following average constitutional formula: (C₃H₇SiO_(3/2))_(x)[C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2)]_(y){R_(c)SiO_((4-c/2))}_(z), where R′, a and b are as defined above; each R is an independently selected phenyl group, alkyl group having 1 to 10 carbon atoms, hydroxyl group, or alkoxy group. Examples of the alkyl group include methyl, ethyl, butyl, hexyl, octyl, and decyl. The most preferable from the point of view of compatibility with component (A) is methyl. Alkoxy groups may be the same as the aforementioned (R′O) groups; c is between 0 and 3; x>0, y>0, z≧0, (x+y+z)=1 and x/(x+y+z)≧0.2. In addition, it is recommended (x+y)/(x+y+z)≧0.4 and more preferably (x+y)/(x+y+z)≧0.6 The weight-average molecular weight of component (B) should be within the range of 800 to 20000, preferably 1000 to 8000. Examples of component (B) include the following organopolysiloxane resins where a is 1 or 2 and b is 1 or 2: (C₃H₇SiO_(3/2))_(0.5)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.3)[C₃H₇(C₂H₅O)_(b)SiO_((3-b)/2)]_(0.2), (C₃H₇SiO_(3/2))_(0.4)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.4)[C₃H₇(C₃H₇O)_(b)SiO_((3-b)/2)]_(0.2), (C₃H₇SiO_(3/2))_(0.4)(CH₃SiO_(3/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C_(3H) ₇O)_(b)SiO_((3-b)/2)]_(0.08), (C₃H₇SiO_(3/2))_(0.4)((CH₃)₂SiO_(2/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C₃H₇(C₄H₉O)_(b)SiO_((3-b)/2)]_(0.08), and (C₃H₇SiO_(3/2))_(0.4)(C₆H₅SiO_(3/2))_(0.2)[C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.32)[C₃H₇(C₃H₇O)_(b)SiO_((3-b)/2)]_(0.08)

Component (B) is obtained by hydrolyzing an organoalkoxysilane or organoalkoxysilanes. For example, it can be produced by hydrolyzing propyltrimethoxysilane, propyltriethoxysilane, propyltri(n-propoxy)silane, propyltri(i-propoxy)silane, or by co-hydrolyzing the aforementioned propylalkoxysilanes with various alkoxysilanes. Examples of these alkoxysilanes include methyltrimethoxysilane, methlyltriethoxysilane, methyltri(i-propoxy)silane, dimethyldimethoxysilane, and phenyltrimethoxysilane. The propyltrichlorosilane can also be hydrolyzed in the presence of alcohol. In this case, co-hydrolyzation can be carried out by adding methyltrichlorosilane, dimethyldichlorosilane, phenyltrichlorosilane, or similar chlorosilanes and methyltriethoxysilane, methyltriethoxysilane, methyltri(i-propoxy)silane, or similar methylalkoxysilane. Alcohols suitable for these purposes include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, butanol, methoxy ethanol, ethoxy ethanol, or similar alcohols. Examples of hydrocarbon-type solvents which can also be concurrently used include toluene, xylene, or similar aromatic hydrocarbons; hexane, heptane, isooctane, or similar linear or partially branched saturated hydrocarbons; and cyclohexane, or similar aliphatic hydrocarbons.

Component (B) should be used in an amount of 0.5 to 100 parts by weight, preferably 10 to 70 parts by weight for each 100 parts by weight of component (A). If it is used in an amount smaller than the lower allowable limit, it will not be able to reveal its properties. If, however, it is used in an amount exceeding the upper recommended level, too much of component (B) will adhere to the treated product.

The composition of the invention is produced by merely mixing the aforementioned components (A) and (B). If necessary, in addition to the aforementioned components, the composition of the invention may be compounded with various additives. Such additives may include metal salts of higher fatty acids that antistick characteristics to the fiber yarn, for example magnesium stearate, zinc stearate, calcium stearate, and barium stearate. If necessary, the composition can be combined with anti-corrosive agents and charge-resistant agents. However, the composition should not contain ether-modified polyorganosiloxanes, such as polyorganosiloxane modified with ethylene oxide or polyorganosiloxane modified with propylene oxide.

Fiber yarn may be treated with the compositions, for example, by immersion in a treatment bath of the compositions of the invention followed by roll expression, or by bringing the running fiber yarn into contact with pick-up rolls. The generally preferred add-on amount for the composition of this invention may be different depending on the type of the fiber yarn but it is preferably within the range of 0.05 to 9.0 wt. %. Types of fiber yarn that can be treated with compositions of the invention include for example, natural fibers such as wool, silk, flax, cotton, angora, and mohair; regenerated fibers such as Rayon and Bemberg; semi-synthetic fibers such as acetate; and synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyvinyl chloride, vinylon, polyethylene, polypropylene, and polyurethane (Spandex). As used herein, the word “yarn” refers to continuous filament thread, spun yarn, or tow.

The straight-oil treatment composition described above is characterized by improved antistatic properties, excellent compatibility with other components, and improved storage stability. This is achieved due to the use of the component (B) having a specific molecular structure. Furthermore, since component (B) can be synthesized at a relatively low cost, the composition of the invention can be advantageously used in commercial production.

The invention will now be described with reference to practical examples. In the examples hereinbelow, “parts” denotes “weight parts”, “%” denotes “weight %”, and the viscosity is the value at 25° C. The storage stability and compatibility were measured by the methods described below.

Compatibility—Immediately after preparation, 20 cc of the straight-oil fiber treatment composition was placed in a glass bottle, and its appearance was visually inspected. The compatibility was rated according to the following scale:

-   ∘: denotes homogeneous dissolution and transparency -   Δ: denotes slight white turbidity -   X: denotes significant white turbidity

Storage Stability—The straight-oil fiber treatment composition was placed in a glass bottle and stored for 1 week at 25° C. and then was inspected visually. The storage stability was rated according to the following scale:

-   ∘: denotes homogeneous dissolution and transparency -   Δ: denotes slight separation and precipitation -   X: denotes significant separation and precipitation

SYNTHESIS EXAMPLE 1

A four-neck flask equipped with a cooling pipe, thermometer, and a stirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g of toluene. While the components were stirred, a mixture of 137 g of water and 317 g of isopropyl alcohol was added dropwise. Upon completion of the addition, the mixture was heated to 70° C. and stirred for 30 min. The mixture was then cooled, and the separated water layer was removed. The organic layer was then washed three times with water. The product was combined with 1000 g of water in which 10 g of sodium hydroxide was dissolved, and the components were mixed for 1 hour and washed three times with water. The cooling tube was replaced with a water separation tube, the product was heated, water was azeotropically removed, the solvent was removed by stripping, and, as result, a highly viscous organopolysiloxane was obtained. Analysis using ¹³C-NMR, ²⁹Si-NMR, and GPC showed that the obtained organopolysiloxane resin (TP-1) with a weight-average molecular weight of 4800 was represented by the following constitutional formula: (n-C₃H₇SiO_(3/2))_(0.58) [n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.31) [n-C₃H₇O)_(b)SiO_((3-b)/2)]_(0.11), where a=1 or 2, and b=1 or 2.

SYNTHESIS EXAMPLE 2

A four-neck flask equipped with a cooling pipe, thermometer, and a stirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g of toluene. While the components were stirred, a mixture of 137 g of water, 18 g of methyl-triisopropoxysilane, and 300 g of isopropyl alcohol was added dropwise. Upon completion of the addition, the mixture was heated to 70° C. and stirred for 30 min. The mixture was then cooled, and the separated water layer was removed. The organic layer was &en washed three times with water. The product was combined with 1000 g of water in which 10 g of sodium hydroxide was dissolved, and the components were mixed for 1 hour and washed three times with water. The cooling tube was replaced with a water separation tube, the product was heated, water was azeotropically removed, the solvent was removed by stripping, and, as result, a highly viscous organopolysiloxane was obtained. Analysis wing ¹³C-NMR, ²⁹Si-NMR, and GPC showed that the obtained organopolysiloxane resin (TP-2) with a weight-average molecular weight of 4000 was represented by the following constitutional formula: (n-C₃H₇SiO_(3/2))_(0.54)(CH₃SiO_(3/2))_(0.1) [n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.27) [n-C₃H₇(i-C₃H₇O)_(b)SiO_((3-b)/2)]_(0.09), where a=1 or 2, and b=1 or 2.

SYNTHESIS EXAMPLE 3

A four-neck flask equipped with a cooling pipe, thermometer, and a stirrer was loaded with 722 g of n-propyltrichlorosilane and 488 g of toluene. While the components were stirred, 137 g of water was added dropwise. Upon completion of the addition, the mixture was heated to 70° C. and sired for 30 min. The mixture was then cooled, and the separated water layer was removed. The organic layer was then washed three times with water. The product was combined with 1000 g of water in which 10 g of sodium hydroxide was dissolved, and the components were mixed for 1 hour and washed three times with water. The cooling tube was replaced with a water separation tube, the product was heated, water was azeotropically removed, the solvent was removed by stripping, and, as result, a highly viscous organopolysiloxane was obtained. Analysis using ¹³C-NMR, ²⁹Si-NMR and GPC showed that the obtained organopolysiloxane resin (TP-3) with a weight-average molecular weight of 5000 was represented by the following constitutional formula: (n-C₃H₇SiO_(3/2))_(0.64) [n-C₃H₇(HO)_(a)SiO_((3-a)/2)]_(0.36),

where a=1 or 2.

PRACTICAL EXAMPLE 1

A straight-oil fiber treatment composition was prepared by uniformly mixing 30 g of the organopolysiloxane resin (TP-1) obtained in Synthesis Example 1 and 70 g of liquid paraffin having a viscosity of 12 mm²/s. The obtained straight-oil fiber treatment composition comprised a transparent solution having a viscosity of 24 mm²/s, a specific gravity of 0.87, and a refractory index of 1.453. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured with the use of a volume-resistivity measurement instrument of Hewlett Packard Co. by a method for measuring volume resistivity (250V/1 min) specified by JIS C2101. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 2

A straight-oil fiber treatment composition was prepared by uniformly mixing 30 g of the organopolysiloxane resin (TP-1) obtained in Synthesis Example 1 and 70 g of liquid paraffin having a viscosity of 17 mm²/s. The obtained straight-oil fiber treatment composition comprised a transparent solution having a viscosity of 30 mm²/s, a specific gravity of 0.91, and a refractory index of 1.456. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 3

A straight-oil fiber treatment composition was prepared by uniformly mixing 10 g of the organopolysiloxane resin (PIT-1) obtained in Synthesis Example 1 and 90 g of liquid paraffin having a viscosity of 12 mm²/s. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 4

A straight-oil fiber treatment composition was prepared by uniformly mixing 20 g of the organopolysiloxane resin (TP-1) obtained in Synthesis Example 1 and 80 g of liquid paraffin having a viscosity of 12 mm²/s. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 5

A straight-oil fiber treatment composition was prepared by uniformly mixing 30 g of the organopolysiloxane resin (TP-2) obtained in Synthesis Example 2 and 70 g of liquid paraffin having a viscosity of 12 mm²/s. The obtained straight-oil fiber treatment composition was transparent. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

PRACTICAL EXAMPLE 6

A straight-oil fiber treatment composition was prepared by uniformly mixing 30 g of the organopolysiloxane resin (TP-1) obtained in Synthesis Example 1 and 70 g of an oil of polydimethylsiloxane having both molecular terminals capped with trimethylsiloxy groups and having a viscosity of 10 mm²/s. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

COMPARATIVE EXAMPLE 1

A straight-oil fiber treatment composition was prepared by uniformly mixing 30 g of the organopolysiloxane resin (IP-3) obtained in Synthesis Example 3 and 70 g of liquid paraffin having a viscosity of 12 mm²/s. The obtained straight-oil fiber treatment composition comprises a semitransparent solution with a noticeable precipitation. Compatibility and storage stability of the obtained straight-oil fiber treatment composition were measured. All results of measurements and evaluation are shown in Table 1.

COMPARATIVE EXAMPLE 2

Storage stability was measured for a strait-oil fiber treatment composition that comprised 100 g only of liquid paraffin of a viscosity of 12 mm²/s. Volume resistivity was measured by the same method as in Practical Example 1. All results of measurements and evaluation are shown in Table 1.

TABLE 1 (A) (B) Storage Volume Type Content % Type Content % Compatibility Stability Resistivity Evaluation Pr. Ex. 1 A-1 70 TP-1 30 ◯ ◯ 2 × 10¹³ Good Pr. Ex. 2 A-2 70 TP-1 30 ◯ ◯ 2 × 10¹³ Good Pr. Ex. 3 A-1 90 TP-1 10 ◯ ◯ 4 × 10¹³ Good Pr. Ex. 4 A-1 80 TP-1 20 ◯ ◯ 3 × 10¹³ Good Pr. Ex. 5 A-1 70 TP-2 30 ◯ ◯ 3 × 10¹³ Good Pr. Ex. 6 A-3 70 TP-1 30 ◯ ◯ 3 × 10¹³ Good Comp. Ex. 1 A-1 70 TP-3 30 Δ Δ — Unsatisfactory (insufficient compatibility and storage stability) Comp. Ex. 2 A-1 100 — 0 — ◯ 4 × 10¹⁴ Unsatisfactory (insufficient antistatic properties) * Types of component (A): A-1: liquid paraffin of 12 mm²/s viscosity A-2: liquid paraffin of 17 mm²/s viscosity A-3: polydimethylsiloxane oil of 10 mm²/s viscosity

The straight-oil treatment composition of the invention, which has aforementioned main components (A) and (B), is characterized by excellent component compatibility, storage stability, and anti-static properties. 

1. A straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiioxane oil or liquid paraffin having a viscosity of 3 to 70 mm²/s at 25° C.; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups, wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2), and wherein the amount of silanol groups is greater than the amount of the silicon-bonded alkoxy groups.
 2. The straight-oil finishing composition according to claim 1, where said component (A) is liquid paraffin.
 3. A straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiioxane oil or liquid paraffin having a viscosity of 3 to 70 mm²/s at 25° C.: and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups, wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2), and wherein said silicon-bonded alkoxy groups are alkoxy groups having 3 to 8 carbon atoms.
 4. The straight-oil finishing composition according to claim 3, where said component (A) is liquid paraffin.
 5. A fiber yarn treated with the straight-oil finishing composition of claim
 3. 6. A straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiioxane oil or liquid paraffin having a viscosity of 3 to 70 mm²/s at 25° C.; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups and wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2); and where said component (B) contains both siloxane units represented by formula C₃H₇SiO_(3/2) and C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), wherein 20-95 mole % of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2) and 5-80 mole % of all siloxane units are siloxane units represented by formula C₃H₇(HO)_(a)(R′O)_(b)SiO_((3-a-b)/2), where each R′ is independently selected from alkyl groups having 1 to 8 carbon atoms and alkyloxyalkylene groups having 1 to 8 carbon atoms, 0<a≦2, 0<b≦2, 0<(a+b)≦2.
 7. The straight-oil finishing composition according to claim 6, where said component (A) is liquid paraffin.
 8. A fiber yarn treated with the straight-oil finishing composition of claim
 6. 9. A straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiioxane oil or liquid paraffin having a viscosity of 3 to 70 mm²/s at 25° C.; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups, wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2), and where said component (B) is represented by the following average constitutional formula: (C₃H₇SiO_(3/2))_(x)[C₃H₇(HO)_(a)(R′O)_(b) SiO_((3-a-b)/2)]_(y){R_(c)SiO_((4-c/2))}_(z), where each R′ is independently selected from alkyl groups having 1 to 8 carbon atoms and alkyloxyalkylene groups having 1 to 8 carbon atoms, and each R is independently selected from phenyl groups, alkyl groups having 1 to 10 carbon atoms, hydroxyl groups, and alkoxy groups, 0<a≦2, 0<b≦2, 0<(a+b)≦2, c is between 0 and 3, x>0, y>0, z≧0, (x+y+z)=1, and x/(x+y+z)≧0.2.
 10. The straight-oil finishing composition according to claim 9, where said component (A) is liquid paraffin.
 11. A fiber yarn treated with the straight-oil finishing composition of claim
 9. 12. A fiber yarn treated with the straight-oil finishing composition comprising (A) 100 parts by weight of a polydimethylsiioxane oil or liquid paraffin having a viscosity of 3 to 70 mm²/s at 25° C.; and (B) 0.5 to 100 parts by weight of an organopolysiloxane resin, which contains silanol groups and silicon-bonded alkoxy groups and wherein 20 mole % or more of all siloxane units are siloxane units represented by formula C₃H₇SiO_(3/2).
 13. A fiber yarn according to claim 12, where said component (A) is liquid paraffin. 